Paper SS1-MoA6
Microcanonical Transition State Theory: Closing the "Nonequilibrium Gap" Between Surface Science, Catalysis, and Electronic Structure Theory
Progress towards achieving a unified kinetic picture of surface reactions has been uneven when nonequilibrium surface science and thermal equilibrium catalysis experiments have been compared and contrasted with electronic structure theory (EST) calculations of transition state characteristics. A simple microcanonical unimolecular rate theory (MURT) model of gas-surface reactivity has been able to largely close this "nonequilibrium gap" for several activated dissociative chemisorption reactions [e.g., CH@sub 4@ on Ni(100), Pt(111), and Ir(111); SiH@sub 4@ on Si(100); H@sub 2@ on Cu(111)]. The MURT's ability to quantitatively predict and directly compare the results of disparate equilibrium and nonequilibrium experiments to one another and to the calculations of EST will be shown to open up some useful new opportunities to rigorously test and refine our understanding of reactive transition states and kinetics at surfaces.